Process for making gasolines of high quality



` Rr'gocnsgfr'lz Mmmm esemgsgz- 31x55 QUALITY originalimd Apri; 15, 19:56-

n r//YG sim/m no Mo dR fun Aftovnej Patented ug. 2 7, 1940 l l UNITED STATES PATENT oFFlcE ritooass rolt MAKING GAsoLlNEs oF HIGH QUALITY Alois Zinke, Graz, Austria, assigner to Reichhold Chemicals, Inc., Detroit, Mich., a corporation of Delaware Original application April 15, 1936, Serial No.

74,595. Divided and this application September 29, 1936, Serial No. 103,213.- In Austria May 7, 1935 l 2 Claims. (Cl. 1536-35) This invention relates to a process for precarbon radicals whilstR" and R" may be such paring gasolinas of high quality, which consists radicals or hydrogen. i in that phenol or its homologues are condensed Now I have found that the cracked gasolines with cracked gasolines which contain compounds are rich in unsaturated non-aromatic compounds 5 having non-aromatic multiple linkages, and in Which are well adapted for the formation of sub- 5 removing the substituted'phenols formed. Stituted phenols by lneanS of any of thenlethods The present application is a division of Serial mentioned above. In most cases the said un- No. 74,595, filed April l5, 1936, now Patent No. saturated compounds can be taken up quantita- 2,l54,l92, dated April l1, 1939. tively by the phenol or at least mainly. An object of my invention consistsin prepar- My invention is not only of great importance 10 ing gasolines, of high quality which are substansince valuable substituted phenols are obtained tially free from compounds having unsaturated in a very economical Way but also due to the non-aromatic linkages. fact that the hydrocarbons which did not enter Another object of my invention consists in prethe reaction are no more deferiorated by the paring phenols which are substituted by one or disturbing odor of cracked sasolines- Depending more hydrocarbon radicals having a relatively upon the source and still more upon theprocess high number of aliphatic or clicycllc c-atoms, of the preparation of the cracked gasoline these which phenols may serve for the preparation ofabove mentioned remaining hydrocarbons conoil-soluble phenolic resins. This object forms sist almost entirely of benzene and its homologues so the subject matter of my patent No. 2,154,192 or of mixtures thereof with hydrocarbons of referred to above. paraflin nature or also' mainly of the latter. I

Condensation between the phenols and the un- Wish to mention particularlyr that all those unsaturated hydrocarbons is 4theoretically possible Saturated hydrocarbons Which tend to autoreSinby the use of various contact agents such as cation owing to a plurality of double linkages sulfuric or hydrochloric acid with or without the participate in theireactlon- It iS apparent that 25 addition ofglacial acetic acid, halides off alutheir elimination from cracked gasoline which mlhium, iron, zinc and the like ln conjunction serves as fuel for internal combustion engines with hydrogen halides. Instead of` hydrogen is of great technical importancehalide any reactive hydrocarbon halide may serve When using anhydrous aluminum or ferric for starting the reaction. chloride or other analogically behaving metal 30 According to thepresent invention, howeve halides the 'condensation reaction is easily per- I proceed according to the method of Friedl formed. In this oase the addition of hydrogen crafts, .employing a metal halide catalyst such halide may be dispensed with since traces thereof as anhydrous aluminum or ferrie chloride, and are usually formed due to the influences of hund that markedly improved technical results midity on .the metal halide; Zinc chloride and 35 are obtained where proceeding according to this other similarly behaving metal halides render the method. y addition of a hydrogen halide necessary. It is, The accompanying drawing is a, ow sheet of however, more advisable to use the latter in the complete process of the present invention. statu nascondi, which can be done e. g. by co- 40 Not all unsaturated hydrocarbons are equally employing an acyl halide or more suitably a 40 capable of undergoing such reactions; those hyreadily reactive hydrocarbon halide. Such a drocarbons apparently'are mainly suited which halide is e. g. a tertiary hydrocarbon halide or by chemical addition of hydrogen halide or water benzylchloride and the like. form tertiary compounds. Thus such olenic or For my process I may use common phenol,

polyolelnic substances are particularly adapted or its homologues, such as the cheap technical 45 to undergo the said condensation reaction in mixtures of cresols,xylenols; naphthols; polyoxywhich the double linkages are located at tertiary benzenes and polyvalent polynuclear phenols,

carbon atoms, i. e. the substances should contain e. g. dioxynaphthalenes. If substituted phenols one or more groups as indicated by the formula intended for the preparation of pale resins are aimed at 'I prefer the use of common phenol and 5o R /R of cracked gasolinas which do not contain IJ=o v l polyolenic substances. The substituted phenols f \R obtained are readily and almost quantitatively distillable and are practically colorless in the dis- 55 in which R and R' represent monovalent hydrotilled form. On the contrary substituted phenols 5l linkages are, if

. hind as a non-distillable, hard, resinous residue.

This residue mayalso be immediately employed in the varnish industry particularly due to its very good solubility in drying oils. Resins of this kind having a pronounced phenolic char- Y acter are often of particular value and importance in preparing oil varnishes.

While the condensation between the phenol and the monoolei'lnic portion of a cracked gasoline apparently takes place in practically invariable stoichiometric proportions i. e. more or less independent of the proportions employed, the polyolefinic hydrocarbons may interact with the phenol in various proportions. The ratio in which the components enter into combination within certain limits depends on the proportions used, the catalyst employed and the reaction temperature. The condensation reaction between the phenol and the polyoleiine probably takes place in individual steps i. e. initially only by the mediation of a single double linkage; the phenolic body formed having an unsaturated substituent then polymerizes by the action of the catalyst (metal halide and hydrogen halide); or

there may also be formed .chain-like macro-molecules in consequence of the plurality of reactive places both in the polyoleilne and in the phenol. The higher boiling polyoleiinic portions of cracked gasolines are capable of yielding solid resins readily soluble in fatty oils directly (i. e. without eliminating low molecular condensation products by distillation in` vacuo), particularly if relatively small proportions of phenol are employed. f

The most volatile portions of cracked gasolines, which have a very low boiling point and may be gaseous at room temperature, predominantly consist of unsaturated hydrocarbons having up to iive carbon atoms. On passing hydrogen halide through the mixture of phenol and cracked gasoline they escape to a large extent if no special provision is taken.' It vis e. g. advisable to conduct them in conjunction with hydrogen halide over suitable contact agents and to separately collect the alkyl halides formed hereby and to condense only these with the phenol. The same reaction may of course also be carried out with all of the gasoline, this, however, being of no advantage as compared with directly reacting the phenol with unsaturated hydrocarbons. They may also be passed through phenol in excess or more suitably through a reaction mixture in which in addition thereto there is formed hydrogen halide in statu nascendi. These volatile oleiines may also be retained in another way viz. in that they are e. g. passed through tertiary alcohols. These are like all alcohols suitable sol- Vents, and by the action of hydrogen halide not only the tertiary halide corresponding to the alcohol but simultaneously also the addition product from hydrogen halide and oleflne is formed. The volatile olenes may also be collected in a sufficient quantity of certain hydrocarbons such as dipentene, which, owing to their structure, are capable of forming addition products of hydrogen halide which in turn readily enter into reaction with phenol. The absorbed olenes then readily take part in this reaction which is due to the hydrogen halide in statu nascendi.

I wish to be understood that the following examples are only of illustrative character and that my invention is not restricted to the special features. A very large number of cracking processes are known, which may be perhaps divided into several characteristic groups. According to one process cracking is performed in the liquid phase with the application of more or less high pressure in the absence oi' special catalytic agents. The processes according to Ellis, Dubbs, Burton and others apparently are the most developed ones and may be regarded as representatives of this group. The cracked gasolinas obtained by a process of this group contain saturated hydrocarbons and a varying proportion of olenic hydrocarbons whilst no or only small proportions of aromatic hydrocarbons are present. Another method, of which the processes developed by Gyro or by Knox may be regarded as examples consists in exposing the oils to be cracked to particularly high temperatures in the vapor phase generally without application of pressure. Slightly active contact masses may be present in some of these processes. The gasolines obtained are particularly rich in unsaturated hydrocarbons which mainly consist of oleiinic, polyolerlnic and aromatic hydrocarbons. A third group is characterised by the use of highly active catalysts such as aluminum chloride and by the application of relatively low temperatures mostly without pressure. The gasolines obtained have a relatively very low proportion of unsaturated hydrocarbons and therefore are of only poor interest for my process.

Finally I wish to state that any cracked gasoline rich in unsaturated non-aromatic hydrocarbons is suited for my process irrespectivex of the method according to which it has been prepared and the origin of the stuiis which have been cracked. Such stuffs are in the first place those petroleum fractions of low value, more particularly the so-called gas oil, which in general can neither be used as motor fuel nor for lubricating purposes and mostly serve as fuel oil; but also other oxygen-free or oxygen-,containing more or less high molecular organic comp'ounds of vegetable or animal origin, such as bituminous oils (shale oil, shale tar oil) or similar products such as are obtained from low-temperature carbonization of brown or blackcoal; waste fats and fatty oils.

Example 1 Gaseous hydrogen chloride is passed through a mixture of 1000 grms. gasoline of American origin obtained by crackinghigh boiling fractions of petroleum under pressure at temperatures surpassing 400 C. and in the absence of catalysts, 700 grms. phenol and 40 grms. aluminum chloride. The temperature is then increased to C. andv maintained for 16 hours. Thereupon the reaction mixture is freed from the portions of the gasoline and the phenol, which did not enter into reaction, by means of a current of steam; the separation may also be effected after washing by commondistillation and subsequent vacuum distillation.

Thus about 380 grms. of gasoline which did not enter into reaction, 295 grms. of unaltered phenol and '705 grms. of a mixture of substituted phenols are obtained. The latter is of brown color and may be distilled in vacuo almost cornpletely whereby a colorless product is obtained which is particularly suited for the preparation of oil soluble formaldehyde resins. The main mmsi).

Vso

quantity pass/es over between 150 and 250i C. (12

.The specific gravity oiythe original cracked gasoline is W123/15 C. The'gasoline contains about per cent.- unsaturated hydrocarbons, partly of aromatic; mainly, however, of oleilnic nature, and about 40 per cent saturated hydrocarbons. The specific gravity of the recovered gasoline is 0.786/ 15 C. This gasoline consists of about 15per cent unsaturated, mainly aromatic hydrocarbons and of about per cent paraflinhydrocarbons. It is completely relieve'dof the penetrating odor of the cracked gasoline.

The gaseous portions, i. e. about 320 grms., which escape on carrying through the condensation, may be utilized in the way described in Example V2. The condensation reaction may also be carried through at lower temperature e. g. atv

40 C., the reaction period -being then suitably substantially protracted. The loss in gaseous portionsis then substantially smaller. In this way also substituted phenols are obtained which yield aldehyde resins being by vfar more lightproof.

When replacing the cracked gasoline used in this example by any other obtained in an equivalent way, also if it is of another origin, e. g. Roumanian,- very similar results are obtained.

Example 2 The portions of the cracked gasoline passing over with the current of hydrogen' chloride on carrying through the Example 1 are conducted together with the latter over a contact mass consisting of asbestos carrying bismuth chloride and collected in a receiver cooled by ice. The condensate obtained is brought into reaction with 200 grms. phenol in the presence of each 5 grms. aluminum chloride and zinc chloride at 60 C for l2 hours. Instead of separately collecting the vaporsin a receivercooled by ice they may also be directly conducted into the phenol ln the presence of the catalysts mentioned. The escaping vapors are conducted through a second receiver which is warmed at 50-60 C. and loaded with 6 grms.A aluminum chloride and 100 grms. phenol.

After washing the reaction mixture with water and suitable further working up, about grms. of gasoline not entered into reaction, grms. unaltered phenol and 250 grms. substituted phenols as well as about 10 liter of gaseous portions are obtained. 'I'he mixture of substituted phenols is of light brown color and after distillation in vacuo almost colorless. Afteriprotracted standing crystalline portions separate out which` consist of p-tert. amylphenol.

The liquid or gaseous portions of the cracked gasoline, which did not enter into reaction, contain traces of halogen compounds. In case they are intended to be employed as motor fuel a Afurther suitable treatment with alkalies is still required.

Eample 3 Gaseous hydrogen chloride is passed through a mixture of 150 grms. U. S. P. cresol and each 4 grms. aluminium chloride and zinc chloride to the point of saturation (about 40 grms. being required therefore). 200 grms. oi the cracked gasoline employed according to Example 1 are gradually added andthe temperature is then increased to 50 C. and maintained for 12 hours. After suitably working up the reaction mixture about 85 grms. gasoline, 45 grms. cresol not entered into reaction and 90 grms. of a mixture of relatively high substituted phenols are obtained. About 10l literof gaseous portions (about 30 grms.) escape during the condensation. The mixture of substituted cresols is of rather pa1e brown color and of middle-viscous appearance. They portion o! the'U. S. P.r cresol which did not enter into reaction contains only alittle m-cresol. The recovered gasoline shows equally advantageous properties and quite similar constituents as that obtained according to Example 1.

1000 grms.l of cracked gasoline of American ori- I g'in which is obtained lby cracking gas oil in the l .also in this case remain uncombined are freed from hydrogen chloride and collected in a gasometer.

When worked up' in a way as described in Ex. ample 1, about 810 grms. of substituted phenols which almost completely have been formed in the first reaction vessel,A 400 grms. of phenol not entered into reaction and 360 grms. of portions of the cracked gasoline notentered into reaction'are obtained. yAbout 20 liter gaseous portions are collected in the gasometer.

The substituted phenols are of dark brown color and of viscous appearance. If subjected to distillation in vacuo 45-50 per cent of the phenols may be obtained in the form of a light colored'distillate boiling between 100 and 250 C. (12 mms). The portions having the lowest boiling point are thinly liquid, those having a higher boiling point viscous to resinous. The residue consists of a hard,l dark resin which e. g. is readily soluble in drying oils and which may directly be employed forthe preparation of oil varnishes in an advantageous manner. This specific gravity of the portions of the cracked gasoline which did not enter into reaction is 0.873. This gasoline almost completely consists of benzene and homologues. They are absolutely free of the, particularly disagreeable odor of the original cracked gasoline, the specific gravity of which is 0.838.

Example 5 large parts by distillation up to 85 C. About.5

per cent of gaseous portions are collected separately.

500 `grms. of the fraction boiling up to 85 C., 200 grms. of phenol and 6 grms. of zinc chloride are warmed up to 40 C. and 10 grms. of tert. butylchloride are added gradually. Thereupon the reaction mixture is maintained at this temperature for further 48 hours.

About 280 grms. of substituted phenols, 90 grms. of phenol not entered into reaction and 300 grms. of unaltered portions of the fraction of the cracked gasoline in addition to 10 liter of gaseous portions which have already been collected during the reaction, are obtained after suitably working up the reaction mixture.

The substituted phenols obtained according to this example are of dark brown color. Also after distillation in vacuo there remains a considerable amount of a hard rcsinous residue of similar properties as that obtained according to Example 4.

The liquid portions of the cracked gasoline which did not enter into reaction almost `com plctely4 consist of benzene. Under otherwise equal conditions the yield oi substituted phenols is only about.50 grms. if no butyl chloride is coemployed; the yield is not substantially increased even if hydrogen chloride or the like is simultaneously employed. Instead .of tert. butyl-chloride there may also be employed another tertiary chloride or a tertiary dichloride, such as dipentene dihydrochloride, or benzyl chloride and the like. When employing aluminium chloride instead of zinc chloride, however, the yield of substituted phenol is about equal to that achieved hereinbefore by means of zinc chloride and butyl chloride, also without employing butyl-chloride or similarly acting halides.

Eample 6 6 grms. of aluminum chloride are added in small portions to a mixture of 200 grms. of the fraction boiling above 85 C. of a cracked gasoline of American origin and 100 grms. of technical Xylenol boiling between 207 and 217 C. The mixture is heated for 48 hours at 50-60" C. after the considerable self-hardening has ceased.

The reaction mixture is freed from the unaltered portions of the cracked gasoline (120 grms.) by distillation after having been washed with water. These portions almost completely consist of toluene and xylenes. The remaining mixture ol substituted phenols (175 grms.) together with unaltered portions of xylenols-contained therein may serve for the production of 500 grms. of the gasoline fraction used in Example 6 are condensed with 100 grms. of phenol by adding 2 grms. of zinc chloride and 2 grms. of ferric chloride and grms. of dipentene hydrochloride obtained by introducing hydrochloric acid into dipentene. The condensation is rst carried out at about 60 C. in a flask provided with areux condenser, the temperature being raised after a few hours at about 100 C. and maintained for 24 hours. A small portion `of the low boiling inactive part of the gasoline is distilled off hereby. After washing the reaction mixture and distilling oi the portion of the gasoline which did not enter into condensation reaction, about 300 grins. of a hard resin are obaaiaaou tained, which is readily soluble in drying oils and petroleum hydrocarbons. The phenol has been compounded practically'quantitatively. The uncombined part of the'gasoline mainly consists. of aromatic hydrocarbons and only to a very small extent of olenic, apparently monoolenic hydrocarbons, which, however, are free of any disturbing odor.

Example 8 100 grms. of dihydroxy naphthalene (1.8) are condensed in a way analogous to that described in the preceding example with 300 grms. .of the total fraction boiling above 100 C. of a cracked gasoline of the type described in Example 1. About 200 grms. of a viscous phenolic condensation product are obtained which can not be distilled without decomposition. It may serve for the preparation of aldehyde resins showing special properties.

When employing e. g. sulfuric acid as condensing catalyst there are not only much greater technical difficulties to. overcome, but the products obtained are mostly also much darker than these prepared according to the method of Friedl-Crafts. My process may be carried out on commercial scale in iron apparatus. This does not only constitute an economic advantage but the process is also particularly readily performed in the presence of iron.

In the following claims the term cracking gasoline is intended also to comprise a technical mixture of substances comprising gaseous and liquid stuis which contain a substantial proportion of compounds having at least one non-aromatic multiple linkage, and which are obtained by thermic decomposition, of higher molecular substances such as shale oils, brown coal tar oils, waste fats.

What I claim is:

1. A process for preparing a gasoline mainly consisting of aromatic hydrocarbons, which consists in reacting with the aid of a condensing catalyst being a member of a group consisting of aluminum, iron and zinc halides, at .temperatures ranging from room to boiling temperature and during a prolonged period of time (1) a cracking gasoline obtained by cracking in the vapor phase with (2) a phenol in such quantity as to combine therewith substantially al1 oleflnic and polyolenic compounds, and removing any excess phenol and the substituted phenols formed.

2. A process according to claim 1, in which the non-phenolic final products are treated with alkalies in order to saponify any organic halides present.

ALOIS ZINKE. 

